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| United States Patent |
5,216,074
|
|
Imai
, et al.
|
June 1, 1993
|
Thermoplastic elastomer composition
Abstract
A thermoplastic elastomer composition comprising 99-1 parts by weight of
(i) a hydrogenated diene polymer which is a hydrogenation product of a
straight or branched chain block copolymer consisting of (C) a
polybutadiene block segment having a 1,2-vinyl content of not more than
20% and (D) a block segment which is a polybutadiene or an alkenyl
aromatic compound-butadiene copolymer, the butadiene portion of which has
a 1,2-vinyl content of 25-95% and 1-99 parts by weight of (ii) at least
one of a thermoplastic resin or a rubbery polymer.
| Inventors:
|
Imai; Takateru (Yokkaichi, JP);
Nagano; Masanobu (Yokkaichi, JP);
Mawatari; Masaaki (Suzuka, JP);
Teramoto; Toshio (Yokkaichi, JP);
Hasegawa; Minoru (Suzuka, JP)
|
| Assignee:
|
Japan Synthetic Rubber Co., Ltd. (Tokyo, JP)
|
| Appl. No.:
|
552303 |
| Filed:
|
July 13, 1990 |
Foreign Application Priority Data
| Jul 17, 1989[JP] | 1-182612 |
| Aug 15, 1989[JP] | 1-209608 |
| Current U.S. Class: |
525/66; 524/504; 524/505; 524/525; 524/526; 524/531; 524/555; 525/71; 525/89; 525/93; 525/98; 525/314 |
| Intern'l Class: |
C08L 053/02; C08L 051/04; C08L 077/06; C08L 067/02 |
| Field of Search: |
525/66,71,93,98,314,89
524/525,526,531,555,504,505
|
References Cited
U.S. Patent Documents
| 3634549 | Jan., 1972 | Shaw et al. | 525/314.
|
| 4107236 | Aug., 1978 | Naylor et al.
| |
| 4237245 | Dec., 1980 | Halson et al.
| |
| 4436873 | Mar., 1984 | Furukawa et al. | 525/314.
|
| 4835215 | May., 1989 | Sakano et al. | 525/71.
|
| 4849473 | Jul., 1989 | Cigna et al. | 525/71.
|
| 4902749 | Feb., 1990 | Akkapeddi et al. | 525/71.
|
| 4994508 | Feb., 1991 | Shiraki et al. | 525/71.
|
| 5013790 | May., 1991 | Tung et al. | 525/71.
|
| Foreign Patent Documents |
| 0026292 | Apr., 1981 | EP.
| |
| 0211467 | Feb., 1987 | EP.
| |
| 0270927 | Jun., 1988 | EP.
| |
Other References
World Patents Index Latest, 87-182215, and JP-A-62-112-640, May 23, 1987.
|
Primary Examiner: Seidleck; James J.
Assistant Examiner: Jagannathan; Vasu S.
Attorney, Agent or Firm: Oblon, Spivak, McClelland, Maier & Neustadt
Claims
What is claimed is:
1. A thermoplastic elastomer composition comprising: 99-1 parts by weight
of (i) a hydrogenated diene polymer which is a hydrogenation product of a
straight or branched chain block copolymer consisting of (C) a
polybutadiene block segment having a 1,2-vinyl content of not more than
20% and (D) a block segment which is a polybutadiene or an alkenyl
aromatic compound-butadiene copolymer, the butadiene portion of which has
a 1,2-vinyl content of 25-95%, the block structure of said straight or
branched chain block copolymer being represented by the formula, C-D-C or
(C-D).sub.m -X in which C means the above-mentioned polybutadiene block
segment (C), D means the above-mentioned block segment (D), X means a
coupling residue and m means an integer of 3 or more, at least 90% of the
double bonds in the butadiene portion of the straight or branched chain
block copolymer having been hydrogenated, or (i') a modified hydrogenated
diene polymer in which 0.01 to 10 mole % of at least one functional group
selected from the group consisting of carboxyl group, acid anhydride
group, hydroxyl group, epoxy group, halogen atom and amino group is added
to the hydrogenated diene polymer (i), and 1-99 parts by weight of (ii) at
least one member selected from the group consisting of a thermoplastic
resin and a rubber polymer.
2. The thermoplastic elastomer composition according to claim 1, wherein
component (ii) is a rubbery polymer and at least 10% of the rubbery
polymer has been allowed to gel by subjecting a mixture of component (i)
or (i'), component (ii) and a crosslinking agent for component (ii) to
reaction while applying shear deformation to the mixture.
3. The thermoplastic elastomer composition according to claim 1, wherein
component (ii) is a mixture of at least 10% by weight of the thermoplastic
resin and the rubbery polymer, and at least 10% by weight of a total
amount of component (i) or (i') and the rubbery polymer has been allowed
to gel by subjecting component (i) or (i') and component (ii) to reaction
in the presence of a crosslinking agent while applying shear deformation
to them.
4. The thermoplastic elastomer composition according to claim 1, wherein
the amount of component (i) or (i') is 10-90 parts by weight and component
(ii) is 90-10 parts by weight of a polyolefin resin, and which further
contains (iii) a non-aromatic process oil in a proportion of 1-300 parts
by weight per 100 parts by weight of a total amount of component (i) or
(i') and component (ii).
5. The thermoplastic elastomer composition according to claim 4, wherein at
least 10% by weight of component (i) or (i') has been allowed to gel by
subjecting component (i) or (i'), component (ii) and component (iii) to
reaction in the presence of a crosslinking agent for component (i) or (i')
while applying shear deformation to them.
6. The thermoplastic elastomer composition according to claim 1, wherein
the amount of component (i) or (i') is 5-95 parts by weight and component
(ii) is 95-5 parts by weight of a mixture consisting of 10-90% weight of a
polyolefin resin and 90-10% by weight of an olefinic copolymer rubber and
which further contains (iii) a non-aromatic process oil in a proportion of
1-400 parts by weight per 100 parts by weight of a total of component (i)
or (i') and component (ii).
7. The thermoplastic elastomer composition according to claim 6, wherein at
least 10% by weight of the olefinic copolymer rubber of component (ii) has
been allowed to gel by subjecting component (i) or (i'), component (ii)
and component (iii) to reaction in the presence of a crosslinking agent
for the olefinic copolymer rubber while applying shear deformation to
them.
8. The thermoplastic elastomer composition according to claim 1, wherein
the amount of component (i) or (i') is 5-95 parts by weight and component
(ii) is 95-5 parts by weight of (A) an olefinic polymer having
graft-copolymerized thereon at least one member selected from the group
consisting of a carboxylic acid derivative and an epoxy derivative or the
olefinic polymer having bonded thereto another polymer in the graft or
block form and (B) at least one member selected from the group consisting
of a polyamide polymer and a polyester polymer and which further contains
(iii') a softening agent in a proportion of 0-400 parts by weight per 100
parts by weight of a total of component (i) or (i') and component (ii).
Description
This invention relates to a thermoplastic elastomer composition useful as
interior or exterior parts of automobiles and various industrial parts.
More particularly, this invention relates to a thermoplastic elastomer
composition comprising a thermoplastic elastomer showing excellent
rubber-like properties and a crystalline thermoplastic polymer, which has
properties comparable to vulcanized rubbers.
A hydrogenated block copolymer is known which is obtained by hydrogenating
the butadiene portions of a block copolymer consisting of a polybutadiene
segment of low 1,2-vinyl content and a polybutadiene segment of high
1,2-vinyl content [John Carl Falk and R. J. Schlott, Macromolecules, 4,
152 (1971); Morton et al., ACS Symp. Ser., 193, 101-18 (1982)]. It is also
known that this hydrogenated block copolymer is a thermoplastic elastomer
showing excellent elasticity at room temperature.
The above block copolymer is structurally regarded as consisting of a
polyethylene (PE) and an ethylene-butene copolymer rubber (EB).
However, the thermoplastic elastomer consisting of this block copolymer
(hereinafter referred to as "E-EB type TPE") has drawbacks, for example,
sharp reduction in dynamic strength at high temperatures and the like and
finds no practical application yet in industry.
It is also known that the hydrogenated block copolymer obtained by
hydrogenating the polybutadiene portion of a
polystyrene-polybutadiene-polystyrene block copolymer (the hydrogenated
block copolymer is hereinafter referred to as "SEBS") is a thermoplastic
elastomer showing excellent elasticity at room temperature, similarly to
E-EB type TPE.
A composition consisting of a polypropylene, SEBS and a softening agent in
which the excellent rubbery properties inherent in SEBS are utilized has
excellent elastomer properties and is used in industry. This composition,
however, has insufficient compression set at high temperatures; and when
containing a large amount of a softening agent to allow the composition to
have a low hardness, the composition has slight stickiness at the surface.
Therefore, improvements in these properties have been desired.
This invention aims at solving the above-mentioned technical problems of
the prior art, eliminating the drawbacks of E-EB type TPE which is
intrinsically an excellent thermoplastic elastomer, and thereby providing
an industrially useful material.
This invention provides a thermoplastic elastomer composition [hereinafter
referred to "Elastomer Composition (I)" in some cases] comprising (i)
99-1% by weight of a hydrogenated diene polymer [hereinafter referred to
as "Component (i)" or "Hydrogenated Diene Polymer"] which is a
hydrogenation product of a straight or branched chain block copolymer
(hereinafter referred to simply as "Block Copolymer") consisting of (C) a
polybutadiene block segment (hereinafter referred to as "Block C") having
a 1,2-vinyl content of not more than 20% and (D) a block segment
(hereinafter referred to as "Block D") which is a polybutadiene or an
alkenyl aromatic compound-butadiene copolymer, the butadiene portion of
which has a 1,2-vinyl content of 25-95%, the block structure of said
straight or branched chain block copolymer being represented by the
formula, C-(D-C).sub.n or (C-D).sub.m in which C means the above-mentioned
Block C, D means the above-mentioned Block D, n means an integer of 1 or
more and m means an integer of 2 or more, at least 90% of the double bond
in the butadiene portion of the straight or branched chain block copolymer
having been hydrogenated, and (ii) 1-99% by weight of a thermoplastic
resin, or a rubbery polymer, or both of them [hereinafter referred to as
"Component (ii)" or "Thermoplastic Resin and/or Rubbery Polymer" ].
This invention also provides a modified hydrogenated block polymer
[hereinafter referred to as "Component (i')" or "Modified Hydrogenated
Diene Polymer"] obtained by adding to the hydrogenated diene polymer
[Component (i)], 0.01-10 mole % of at least one functional group selected
from the group consisting of carboxyl group, acid anhydride group,
hydroxyl group, epoxy group, halogen atoms, amino group, isocyanate group
and sulfonate group, as well as a thermoplastic elastomer composition
consisting of Component (i,) and Component (ii).
This invention also provides a thermoplastic elastomer composition
[hereinafter referred to as "Elastomer Composition (II)" in some cases]
obtained by subjecting a mixture of Component (i) or (i'), a rubbery
polymer as Component (ii) and a crosslinking agent for the rubbery polymer
to reaction while applying shear deformation to the mixture, to allow at
least 10% by weight of the rubbery polymer to gel.
This invention also provides a thermoplastic elastomer composition
[hereinafter referred to as "Elastomer Composition (III)" in some cases]
obtained by subjecting Component (i) or (i') and Component (ii) comprising
at least 10% by weight of a thermoplastic resin to reaction in the
presence of a crosslinking agent while applying shear deformation, to
allow at least 10% by weight of the total amount of Component (i) or (i')
and the rubbery polymer to gel.
This invention also provides a thermoplastic elastomer composition
[hereinafter referred to as "Elastomer Composition (IV)" in some cases]
comprising 10-90 parts by weight of Component (i) or (i'), 90-10 parts by
weight of (ii) a polyolefin resin, and 1-300 parts by weight, per 100
parts by weight of the total of Component (i) or (i') and the (ii)
component, of (iii) a non-aromatic process oil.
This invention also provides a thermoplastic elastomer composition
[hereinafter referred to as "Elastomer Composition (V)" in some cases]
obtained by subjecting Elastomer Composition (IV) to reaction in the
presence of a crosslinking agent for Component (i) or (i') while applying
shear deformation, to allow at least 10% by weight of Component (i) or
(i') to gel.
This invention also provides a thermoplastic elastomer composition
[hereinafter referred to as "Elastomer Composition (VI)" in some cases]
comprising 5-95 parts by weight of Component (i) or (i'), 95-5 parts by
weight of (ii) a mixture of 10-90% by weight of a polyolefin resin and
90-10% by weight of an olefin copolymer rubber, and 1-400 parts by weight,
per 100 parts by weight of the total of Component (i) or (i') and the (ii)
component, of (iii) a non-aromatic process oil.
This invention also provides a thermoplastic elastomer composition
[hereinafter referred to as "Elastomer Composition (VII)" in some cases]
obtained by subjecting Elastomer Component (VI) to reaction in the
presence of a crosslinking agent for crosslinking the olefin copolymer
rubber in the (ii) component, while applying shear deformation, to allow
at least 10% by weight of the olefin copolymer rubber to gel.
This invention also provides a thermoplastic elastomer composition
[hereinafter referred to as "Elastomer Composition (VIII)" in some cases]
comprising 5-95 parts by weight of Component (i) or (i'), 95-5 parts by
weight of (ii) a mixture of (A) an olefin polymer having copolymerized
therewith or grafted thereon a carboxylic acid derivative or an epoxy
derivative or both of them, or said polymer having bonded thereto other
polymer in a graft or block form, and (B) at least one polymer selected
from the group consisting of polyamide polymers and polyester polymers [in
the (ii) component, the amount of the (A) component is not more than 50%
by weight], and 0-400 parts by weight, per 100 parts by weight of the
total amount of Component (i) or (i') and the (ii) component, of (iii) a
softening agent.
Component (i), Hydrogenated Diene Polymer used in this invention can be
obtained by hydrogenating a straight or branched chain block copolymer
consisting of a polybutadiene block segment [Block C] having a 1,2-vinyl
content of not more than 20% and a block segment [Block D] which is a
polybutadiene or an alkenyl aromatic compound-butadiene copolymer, the
butadiene portion of which has a 1,2-vinyl content of 25-95%, the block
structure of said straight or branched chain block copolymer being
represented by C-(D-C).sub.n or (C-D).sub.m (C, D, n and m have the same
meanings as defined above).
Block C in Component (i) or (i'), when hydrogenated, becomes a crystalline
block segment having a structure similar to ordinary low density
polyethylene (LDPE).
The 1,2-vinyl content in Block C is usually not more than 20%, preferably
not more than 18%, more preferably not more than 15%.
When the 1,2-vinyl content in Block C is more than 20%, reduction in
crystal melting point after hydrogenation is striking and Component (i) or
(i') has poor dynamic properties.
Block D is a polybutadiene or an alkenyl aromatic compound-butadiene
copolymer and, when hydrogenated, becomes a block segment having a
structure similar to a rubbery ethylene-butene copolymer or alkenyl
aromatic compound-ethylene-butene copolymer.
The alkenyl aromatic compound used in Block D includes styrene,
tert-butylstyrene, .alpha.-methylstyrene, p-methylstyrene, divinylbenzene,
1,1-diphenylstyrene, N,N-dimethyl-p-aminoethylstyrene,
N,N-diethyl-p-aminoethylstyrene, vinylpyridine, etc. Of them, styrene and
.alpha.-methylstyrene are particularly preferable. The amount of the
alkenyl aromatic compound used is not more than 35% by weight, preferably
not more than 30% by weight, more preferably not more than 25% by weight
based on the total weight of the monomers constituting Block D. When the
amount is more than 35% by weight, the glass transition temperature of
Block D gets higher and Component (i) or (i') has poor dynamic properties.
The 1,2-vinyl content of the butadiene portion in Block D is usually
25-95%, preferably 25-90%, more preferably 25-80%, particularly preferably
25-70%. In each case where the content is less than 25% or more than 95%,
the resulting hydrogenated diene polymer shows a crystalline structure
based on a polyethylene chain or a polybutene-1 chain, has resinous
properties, and accordingly has inferior dynamic properties.
The proportions of Block C and Block D in Component (i) or (i') are such
that usually Block C is 5-90% by weight and Block D is 95-10% by weight,
and preferably Block C is 10-85% by weight and Block D is 90-15% by
weight. When Block C is less than 5% by weight and Block D is more than
95% by weight, the amount of crystalline block segment is insufficient and
Component (i) or (i') has poor dynamic properties, which is not
preferable. When Block C is more than 90% by weight and Block D is less
than 10% by weight, Component (i) or (i') has a high hardness and the
resulting composition is unsuited as a thermoplastic elastomer.
In both Hydrogenated Diene Polymer and Modified Hydrogenated Diene Polymer
used in this invention, it is necessary that at least 90%, preferably
95-100% of the double bond in the butadiene portion of Block C and Block D
have been hydrogenated. When less than 90% of the double bond has been
hydrogenated, heat resistance, weather resistance and ozone resistance are
poor.
Block C and Block D both have a weight-average molecular weight of usually
5,000 or more, preferably 10,000 or more, more preferably 15,000 or more.
When the molecular weight is less than 5,000, Component (i) or (i') has
poor dynamic properties.
Block Copolymer consisting of Block C and Block D has a polystyrene-reduced
weight-average molecular weight of 30,000-600,000, preferably
50,000-550,000, more preferably 70,000-500,000. When the molecular weight
is less than 30,000, dynamic properties are insufficient and, when the
molecular weight is more than 600,000, hydrogenation reaction is
difficult.
Hydrogenated Diene Polymer or Modified Hydrogenated Diene Polymer of this
invention can be obtained by forming Block C and Block D by living anionic
polymerization in an organic solvent using an organic alkali metal
compound as an initiator to obtain a block copolymer and then
hydrogenating the block copolymer.
The organic solvent includes hydrocarbon solvents such as pentane, hexane,
heptane, octane, methylcyclopentane, cyclohexane, benzene, xylene and the
like.
The organic alkali metal compound as an initiator is preferably an
organolithium compound.
The organolithium compound is an organomonolithium compound, an
organodilithium compound or an organopolylithium compound. Specific
examples of these include ethyllithium, n-propyllithium, isopropyllithium,
n-butyllithium, sec-butyllithium, tert-butyllithium,
hexamethylenedilithium, butadienyllithium and isoprenyldilithium. The
organolithium compound is used in an amount of 0.02-0.2 part by weight per
100 parts by weight of the monomers.
In the living anionic polymerization, a Lewis base (e.g. ether, amine) can
be used as an agent for controlling the microstructure, i.e. controlling
the vinyl content of conjugated diene portion. The ether specifically
includes diethyl ether; tetrahydrofuran; propyl ether; butyl ether; higher
ethers; and ether derivatives of polyethylene glycols, such as ethylene
glycol dibutyl ether, diethylene glycol diemthyl ether, diethylene glycol
dibutyl ether, triethylene glycol dimethyl ether and the like. The amine
includes tetramethylethylenediamine, pyridine, tertiary amines (e.g.
tributylamine), etc. The Lewis base is used together with the
above-mentioned organic solvent.
The polymerization reaction is effected usually at -30.degree. C. to
+150.degree. C. The living anionic polymerization can be effected by
controlling the system temperature to a given temperature, or allowing the
temperature to rise without removing the heat generated.
Block Copolymer can be produced by any method. In general, however, first
Block C is formed by polymerization in the above-mentioned organic solvent
in the presence of a polymerization initiator such as alkali metal
compound or the like; subsequently, Block D is formed by polymerization.
The thus formed Block Copolymer is reacted with a coupling agent, whereby
Block Copolymer having an extended or branched molecular chain represented
by the following general formula can be obtained:
C-(C-C).sub.n
or
(C-D).sub.m
wherein C and D have the same meanings as defined above, n is an integer of
1 or more, and m is an integer or 2 or more, preferably 2-4.
The coupling agent includes, for example, diethyl adipate, divinylbenzene,
tetrachlorosilicon, butyltrichlorosilicon, tetrachlorotin,
butyltrichlorotin, dimethyldichlorosilicon, methyldichlorosilane,
tetrachlorogermanium, 1,2-dibromoethane, 1,4-chloromethylbenzene,
bis(trichlorosilyl)ethane, epoxidized linseed oil, tolylene diisocyanate
and 1,2,4-benzenetriisocyanate.
The alkenyl aromatic compound content in Block Copolymer can be controlled
by the amount of monomer(s) fed in each polymerization stage, and the
vinyl content in the conjugated diene portion can be controlled by the
amount of the microstructure-controlling agent. The number-average
molecular weight of Block Copolymer can be controlled by the amount of
polymerization initiator (e.g. n-butyllithium) to be added.
The process for producing Block Copolymer used in this invention is
described more specifically below. Block Copolymer can be obtained, for
example, as follows: 1,3-Butadiene for first-stage polymerization is
polymerized in a polymerization solvent, i.e. an organic solvent (e.g.
benzene or cyclohexane) in the presence of an initiator, i.e. an
organolithium compound (e.g. sec-butyllithium) in a high-purity nitrogen
current to form a low-vinyl polybutadiene block (Block C); subsequently, a
microstructure-controlling agent (e.g. tetrahydrofuran or diethyl ether)
and 1,3-butadiene for second-stage polymerization are added and subjected
to polymerization to form a C-D diblock polymer; then, a coupling agent
such as dimethyldichlorosilane or the like is added in a given amount to
subject the C-D diblock polymer to coupling to obtain a C-D-C triblock
polymer.
When there is used a multifunctional coupling agent, there can be obtained
a branched chain multiblock polymer having branches of a plurality of C-D
blocks.
The molecular weight of Block C can be determined by, at the completion of
the first-stage polymerization, taking an appropriate amount of a sample
of the polymerization mixture and subjecting it to gel permeation
chromatography (GPC). Similarly, the molecular weight of the polymer after
the second-stage polymerization can be determined by, at the completion of
the second-stage polymerization, taking an appropriate amount of a sample
of the polymerization mixture and subjecting it to GPC. By subtracting the
molecular weight of Block C from the molecular weight of polymer after the
second-stage polymerization, there can be determined the molecular weight
of the polymer formed in the second-stage polymerization. Therefore, the
molecular weight of Block D in the C-D-C triblock polymer becomes two
times the molecular weight of the polymer formed in the second-stage
polymerization.
By hydrogenating the thus obtained Block Copolymer, there can be obtained
Hydrogenated Diene Polymer used in this invention.
The above hydrogenation is effected by subjecting Block Copolymer to
hydrogenation in an inert solvent in the presence of a hydrogenation
catalyst at 20.degree.-150.degree. C. at a hydrogen pressure of 1-100
kg/cm.sup.2.
The inert solvent used in the hydrogenation includes hydrocarbon solvents
such as hexane, heptane, cyclohexane, benzene, toluene, ethylbenzene and
the like; and polar solvents such as methyl ethyl ketone, ethyl acetate,
diethyl ether, tetrahydrofuran and the like.
The hydrogenation catalyst includes catalysts consisting of a noble metal
(e.g. palladium, ruthenium, rhodium, platinum or the like) supported on
carbon, silica, diatomaceous earth or the like; catalysts consisting of a
complex or rhodium, ruthenium, platinum or the like; catalysts consisting
of (1) a salt of an organic carboxylic acid with nickel, cobalt or the
like and (2) an organoaluminum or an organolithium; hydrogenation
catalysts consisting of (1) a bis(cyclopentadienyl) group-containing
transition metal compound and (2) a reducing organometal compound such as
organoaluminum, organolithium, organomagnesium or the like; and so forth.
Hydrogenated Diene Polymer of this invention can also be produced by
effecting a hydrogenation reaction using a reducing compound (e.g. lithium
aluminum hydride, p-toluenesulfonyl hydrazide or the like), a hydrogen
storage alloy (e.g. Zr-Ti-Fe-V-Cr alloy, Zr-Ti-Nb-Fe-V-Cr alloy,
LaNi.sub.5 or the like) or the like.
The hydrogenation degree of the double bonds of the butadiene portion in
Hydrogenated Diene Polymer of this invention can be controlled by changing
the kind of the hydrogenation catalyst, the amount of the reducing
compound added, the hydrogen pressure in hydrogenation reaction and the
reaction time.
The catalyst residue is removed from the solution containing Hydrogenated
Diene Polymer; a phenol type or amine type antioxidant is added; and from
the resulting polymer solution can be easily isolated Hydrogenated Diene
Polymer.
The isolation of Hydrogenated Diene Polymer can be effected, for example,
by adding acetone, an alcohol or the like to the polymer solution to
precipitate the polymer, or by pouring the polymer solution into boiling
water with stirring to remove the solvent by vaporization.
Modified Hydrogenated Diene Polymer of this invention can be formed by
adding to the above produced Hydrogenated Diene Polymer 0.01-10 mole % of
at least one functional group selected from the group consisting of
carboxyl group, acid anhydride group, hydroxyl group, epoxy group, halogen
atoms, amino group, isocyanate group, sulfonyl group and sulfonate group.
The method for adding the functional group includes, for example:
(1) a method comprising copolymerizing a conjugated diene and an alkenyl
aromatic compound having a functional group in a state that the functional
group is protected, to obtain a block copolymer and removing the
protective group after the completion of the copolymerization.
(2) a method comprising adding a radical-polymerizable monomer having a
functional group to Hydrogenated Diene Polymer by a known graft reaction,
and
(3) a method comprising kneading Hydrogenated Diene Polymer in the presence
of a functional group-containing organic peroxide or azo compound to
effect the addition of the functional group to Hydrogenated Diene Polymer.
Any of these methods can effectively introduce a functional group into
Hydrogenated Diene Polymer. However, the method (2) or (3) is simple and
effective in industrial application.
Modified Hydrogenated Diene Polymer of this invention can be specifically
obtained, for example, by melt-mixing, with heating, Hydrogenated Diene
Polymer and a functional group-containing radical-polymerizable monomer in
the presence of a radical-generating agent (e.g. organic peroxide), or by
melt-mixing, with heating, Hydrogenated Diene Polymer in the presence of a
functional group-containing organic peroxide or azo compound to add an
appropriate amount of the functional group to Hydrogenated Diene Polymer.
The amount of the functional group in Modified Hydrogenated Diene Polymer
is usually 0.01-10 mole %, preferably 0.1-8 mole %, more preferably 0.15-5
mole % based on the molecule constituting Hydrogenated Diene Polymer. When
the amount is less than 0.01 mole %, the compatibility is not improved,
phase separation takes place, and mechanical strengths are poor. When the
amount is more than 10 mole %, no further improvements in compatibility,
etc. are obtained, and side reactions such as gelation and the like tend
to occur during the functional group addition reaction, i.e. the grafting
reaction.
The monomer to be added to Hydrogenated Diene Polymer includes the
followings.
The carboxyl group-containing monomer includes unsaturated carboxylic acids
(e.g. acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric
acid, itaconic acid), etc. and, besides, compounds represented by general
formula (I), etc.:
##STR1##
where R.sup.1 represents a hydrogen atom or a methyl group, R.sup.2
represents an alkylene group of 2-6 carbon atoms, R.sup.3 represents a
phenylene group, a cyclohexylene group, an alkylene group of 2-6 carbon
atoms or an unsaturated hydrocarbon group.
The acid anhydride group-containing monomer includes acid anhydride
compounds such as maleic anhydride, itaconic anhydride, citraconic
anhydride and the like.
The hydroxyl group-containing monomer includes hydroxyl group-containing
alkenyl compounds represented by general formula (II):
##STR2##
wherein R.sup.1 has the same meaning as above, and R.sup.2 represents a
hydrogen atom or an alkyl group of 1-6 carbon atoms.
The epoxy group-containing monomer includes epoxy group-containing alkenyl
compounds represented by the following general formula (III) or (IV):
##STR3##
(R.sup.4 represents a hydrogen atom, a methyl group or a lower alkyl group
substituted with a glycidyl ester group),
##STR4##
(R.sup.4 has the same meaning as defined above).
The halogen atom(s)-containing monomer includes, for example, halogenated
aromatic vinyl compounds such as chlorostyrene, bromostyrene and the like;
and halogenated (meth)acrylates such as 2,4,6-tribromophenyl methacrylate,
2,4,6-trichlorophenyl methacrylate, methyl 2-chloroacrylate, ethyl
2-chloroacrylate, n-butyl 2-chloroacrylate and the like.
The amino group-containing monomer includes, for example, amino group- or
substituted amino group-containing alkenyl monomers represented by general
formula (V):
##STR5##
wherein R.sup.5 represents a hydrogen atom, a methyl group or an ethyl
group, and R.sup.6 represents an alkyl group of 1-12 carbon atoms, an
alkanoyl group of 2-12 carbon atoms, a phenyl group of 6-12 carbon atoms,
a cycloalkyl group or a derivative thereof.
Specific examples of the amino group-containing monomer are aminoalkyl
esters of acrylic acid or methacrylic acid, such as aminoethyl acrylate,
propylaminoethyl acrylate, dimethylaminoethyl methacrylate,
ethylaminopropyl methacrylate, phenylaminoethyl methacrylate,
cyclohexylaminoethyl methacrylate and the like; vinylamines such as
N-vinyldiethylamine, N-acetylvinylamine and the like; allylamines such as
allylamine, methallylamine, N-methylallylamine and the like;
(meth)acrylamides such as acrylamide, methacrylamide, N-methylacrylamide
and the like; and aminostyrenes such as p-aminostyrene and the like.
Preferable examples of the functional group-containing monomer are acrylic
acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride,
glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether,
hydroxyethylene methacrylate, hydroxypropyl methacrylate, hydroxyethyl
acrylate, hydroxypropyl acrylate, and diethylaminoethyl methacrylate.
The functional group-containing monomer further includes, as preferable
examples, substituted arylmaleimide compounds represented by general
formula (VI):
##STR6##
wherein R.sup.7 is a functional group selected from the group consisting
of --OH, --OCH.sub.3, --Cl, --COOH and --NO.sub.2 and is bonded to the o-,
m- or p-position of benzene ring.
Preferable examples of the substituted arylmaleimide compound are
N-(o-carboxyphenyl)maleimide, N-(p-carboxyphenylmaleimide),
N-(p-chlorophenyl)maleimide, N-(m-hydroxyphenylmaleimide) and
N-(p-hydroxyphenyl)maleimide.
The functional group-containing organic peroxide, when decomposed,
generates a free radical containing a functional group such as carboxyl
group, halogen atom, hydroxyl group, epoxy group or the like, and
includes, for example, 2,4-dichlorobenzoyl peroxide, p-chlorobenzoyl
peroxide, succinic acid peroxide, tertbutyl peroxymaleic acid,
cyclohexanone peroxide, methylcyclohexanone peroxide, and tert-butyl
peroxyglycidyl ether.
The functional group-containing azo compound includes, for example,
4,4'-azobis-4-cyanovaleric acid,
2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride,
2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride,
2,2'-azobis[2-(2-imidazolin-2-yl)propane],
2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide
}, 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide},
2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], and
2,2'-azobis[2-(hydroxymethyl)propionitrile].
The functional group-containing organic peroxide or azo compound to be used
for addition of functional group to Hydrogenated Diene Polymer must be
able to effectively generate a free radical at the temperature at which
Hydrogenated Diene Polymer to be subjected to functional group addition is
melted. Some of the functional group-containing organic peroxides or azo
compounds are instable to heat or are decomposed at high temperatures;
accordingly, such peroxides or azo compounds cannot be used when
Hydrogenated Diene Polymer is melted at a high temperature, that is, when
the content of Component (A) in Hydrogenated Diene Polymer is high. For
example, 4,4'-azobis-4-cyanovaleric acid is decomposed at
110.degree.-120.degree. C. and is not suitable for the modification of
Hydrogenated Diene Polymer of high melting temperature.
The thermoplastic resin used as Component (ii) in this invention refers to
all resins which can be melted by heating and molded into any desired
shape. Specific examples of the thermoplastic resin include olefin resins
such as polyethylene, polypropylene, polybutene-1, polymethylpentene,
ethylene-vinyl acetate copolymer and the like; modification products of
these olefin resins with carboxylic acid derivatives or epoxy derivatives;
polyamide resins such as nylon 4,6, nylon 6, nylon 6,6 and the like;
polyester resins such as poly(ethylene terephthalate), poly(butylene
terephthalate) and the like; crystalline thermoplastic resins such as
polyamide elastomer, polyester elastomer and the like; hydrogenation
products of ring-opening polymers of norbornene derivatives, disclosed in,
for example, Japanese Patent Application Kokai No. 01-240517 and Japanese
Patent Application Kokai No. 01-32625; polymers for rubber modification
such as ABS resin, AES resin, AAS resin, MBS resin and the like;
noncrystalline thermoplastic polymers such as acrylonitrile-styrene
copolymer, styrene-methyl methacrylate copolymer, polystyrene, poly(methyl
methacrylate), polycarbonate, poly(phenylene oxide) and the like; and
graft polymers in which on a polymer composed mainly of a repeating unit
of an .alpha.-monoolefin of 2-8 carbon atoms is grafted other polymer, for
example, a graft polymer obtained by grafting an acrylonitrile-styrene
copolymer on an ethylene-propylene copolymer, a graft polymer obtained by
grafting an acrylonitrile-styrene copolymer on an ethylene-butene
copolymer, a graft polymer obtained by grafting butyl acrylate-methyl
methacrylate copolymer on an ethylene-butene copolymer, a graft polymer
obtained by grafting a methyl methacrylate copolymer on an ethylene-butene
copolymer, a graft polymer obtained by grafting a methyl methacrylate
polymer on an ethylene-glycidyl (meth)acrylate copolymer, a graft polymer
obtained by grafting an acrylonitrile-styrene copolymer on an
ethylene-glycidyl (meth)acrylate copolymer, and a graft polymer obtained
by grafting an acrylonitrile-styrene copolymer on a hydrogenation product
of a styrene-butadiene copolymer as disclosed in Japanese Patent
Publication No. 63-32095. Of these thermoplastic resins, olefinic
thermoplastic resins are preferable.
Also, polyamide resins, polyester resins, polycarbonates, polyamide
elastomers, polyester elastomers, etc. are preferable as a component for
improving the heat resistance of the resulting composition. They have
excellent compatibility with Component (i'), in particular.
The rubbery polymer which is another component constituting Component (ii),
refers to all of natural and synthetic rubbers. Typical examples of the
rubbery polymer are styrene-butadiene random copolymer and its
hydrogenation product; isoprene rubber, nitrile rubber and their
hydrogenation products; chloroprene rubber, butyl rubber,
ethylene-propylene rubber, ethylene-propylene-diene rubbers,
ethylene-butene rubber, ethylene-butene-diene rubbers, acrylic rubbers,
.alpha.,.beta.-unsaturated nitrile-acrylic acid ester-conjugated diene
copolymer rubbers, chlorinated polyethylene rubber, fluororubber, silicone
rubber, urethane rubber, polysulfide rubber, styrene-butadiene block
polymer and their hydrogenation products. Of these rubbery polymers,
preferable are essentially saturated rubbers or rubbers of low
unsaturation and modified rubbers obtained by adding a functional group to
them, such as hydrogenation product of styrene-butadiene rubber;
hydrogenation product of nitrile rubber; ethylene-propylene rubber;
ethylene-propylene-diene rubbers; ethylene-butene rubber,
ethylene-butene-diene rubbers; acrylic rubbers, chlorinated polyethylene
rubber, fluororubber, silicone rubber, urethane rubber, polysulfide
rubber, hydrogenation product of styrene-butadiene block polymer, and
.alpha.,.beta.-unsaturated nitrile-acrylic acid ester-conjugated diene
copolymer rubber.
Elastomer Composition (I) comprises, as essential components, (i) a
hydrogenated diene polymer or (i') a modified hydrogenated diene polymer
and (ii) a thermoplastic resin and/or a rubbery polymer. The proportions
of these components are 99-1 part by weight, preferably 95-5 parts by
weight, more preferably 90-10 parts by weight of Component (i) or (i') and
1-99 parts by weight, preferably 5-95 parts by weight, more preferably
10-90 parts by weight of Component (ii) [(i) or (i')+(ii)=100 parts by
weight].
When Component (i) or (i') is used in an amount of more than 99 parts by
weight, the improvement of physical properties is insufficient. When
Component (i) or (i') is used in an amount of less than 1 part by weight,
various elastomeric properties are inferior. When Component (ii) is used
in an amount of less than 1 part by weight, there is seen no improvement
in physical properties due to the addition of Component (ii). When
Component (ii) is used in an amount of more than 99 parts by weight,
features of thermoplastic elastomer are lost.
Component (ii) used in this invention can vary over a wide range, because
Component (i) or (i') which is a hydrogenated diene polymer (E-EB type
TPE) varies over a wide range from a rubbery, very flexible form to a
resinous hard form.
Accordingly, which of a thermoplastic resin, a rubbery polymer or both
should be used as Component (ii), is determined mainly by the properties
of Component (i) or (i') used and the properties of the composition to be
obtained.
Specifically, when the content of Block C in Component (i) or (i') is not
more than 40% by weight, Component (i) or (i') is usually rubbery and
flexible; in this case, therefore, it is desirable that a thermoplastic
resin be used as Component (ii) to obtain a thermoplastic elastomer
composition balanced in properties.
Meanwhile, when the content of Block C in Component (i) or (i') is 60% by
weight or more, Component (i) or (i') shows properties close to those of
resin; in this case, accordingly, it is desirable that a rubbery polymer
be used as Component (ii) to obtain an intended thermoplastic elastomer.
When the amount of Block C in Component (i) or (i') is more than 40% by
weight but less than 60% by weight, it is desirable that a thermoplastic
resin and a rubbery polymer be used in combination as Component (ii) to
obtain a thermoplastic elastomer balanced in overall properties.
The above description on how to combine Component (i) or (i') and Component
(ii) is merely a general description concerning the relationship between
the properties of Component (i) or (i') and the type of polymer to be used
as Component (ii). The composition of this invention is not restricted by
the above description, and Component (ii) can be selected appropriately so
as to provide a desired composition.
The polymer used as Component (ii) may be a mixture of a plurality of
thermoplastic resins and/or a plurality of rubbery polymers.
When Component (ii) is a combination of a thermoplastic resin and a rubbery
polymer, they can be used in any such proportions as to provide a final
composition of desired properties.
Component (i), i.e. the hydrogenated diene polymer has an intrinsic
property of functioning as a compatibilizing agent between different
polymers; therefore, this property can be utilized in formulating the
composition of this invention. It is known that when a block polymer is
used as a compatibilizing agent, about several % by weight is sufficient
as the amount used. In this invention, the minimum amount of Component (i)
or (i') has been specified to be 1% by weight, in consideration of the
role of Component (i) or (i') as a compatibilizing agent.
Therefore, when Component (i) or (i') is used as a compatibilizing agent,
there are used, as Component (ii), a thermopalstic resin and a rubbery
polymer in combination.
In order for Component (i) or (i') to effectively function as a
compatibilizing agent, a particular thermoplastic resin and a particular
rubbery polymer are selected and used in combination.
The thermoplastic resin includes, for example, polyolefin resins such as
polyethylene, polypropylene, polybutene-1 and the like; and graft polymers
in which on a polymer composed mainly of an .alpha.-monoolefin of 2-8
carbon atoms is grafted other polymer. The rubbery polymer includes, for
example, monoolefin copolymer rubbers such as ethylene-propylene rubber,
ethylene-propylene-diene rubbers, ethylene-butene rubber,
ethylene-butene-diene rubbers and the like; chlorinated polyethylene
rubber; hydrogenation product of styrene-butadiene rubber; hydrogenation
product of nitrile rubber; and hydrogenation product of styrene-butadiene
block polymer.
The above-mentioned combination of a particular thermoplastic resin and a
particular rubbery polymer is a combination of polymers having a structure
similar to a polyolefin structure which is the basic structure of the
hydrogenated diene polymer of this invention.
Since the modified hydrogenated diene polymer of this invention has a
functional group, it can act, owing to the chemical reaction between
functional groups, as a compatibilizing agent for polymers which are
ordinarily incompatible with polymers having a polyolefin structure. The
thermoplastic resins which are incompatible with polyolefin resins and on
which the modified hydrogenated diene polymer of this invention can
effectively act as a compatibilizing agent, include polyamide resins such
as nylon 4,6, nylon 6, nylon 6,6 and the like; polyester resins such as
poly(ethylene terephthalate), poly(butylene terephthalate) and the like;
polycarbonates; polyamide elastomers; polyester elastomers; and so forth.
The rubbery polymers incompatible with polyolefin resins include acrylic
rubber, epichlorohydrin rubber, .alpha.,.beta.-unsaturated nitrile-acrylic
acid ester-unsaturated diene copolymer rubbers, urethane rubber, etc.
When Component (i) or (i') is used as a compatibilizing agent, there may be
used other thermoplastic resins, and/or other rubbery polymers in addition
to the above-mentioned resins and polymers.
In the thermoplastic elastomer compositions of this invention comprising
Component (i) or (i') and Component (ii), when (1) Component (ii)
comprises a rubbery polymer as an essential component, (2) a crosslinking
agent for the rubbery polymer is incorporated, and (3) the composition is
subjected to reaction while applying shear deformation, to allow at least
10% by weight of the rubbery polymer to gel, there can be obtained an
elastomer composition [Elastomer Composition (II)] having excellent
dynamic properties.
The crosslinking agent can be crosslinking agents ordinarily used in
crosslinking of rubbers, i.e. those described in, for example,
"Crosslinking Agents Handbook" (by Shinzo Yamashita and Tosuke Kaneko,
published by Taiseisha).
The crosslinking agent is preferably sulfur; sulfur compounds;
p-benzoquinone dioxime; p,p'-dibenzoylquinone dioxime;
4,4'-dithio-bis-dimorpholine; poly-p-dinitrosobenzene;
tetrachlorobenzoquinone; resin crosslinking agents such as
alkylphenol-formaldehyde resin, brominated alkylphenol-formaldehyde resin
and the like; ammonium benzoate; bismaleimide compounds; diepoxy
compounds; dicarboxylic acid compounds; diol compounds; diamine compounds;
amino compounds; organometal salts; metal alkoxides; organometal
compounds; organic peroxides; and so forth.
These crosslinking agents can be used alone or in admixture. Some
crosslinking agents can be used in combination with other compounds to
carry out crosslinking at a higher efficiency.
Specifically, when sulfur or a sulfur compound is used as a crosslinking
agent, it is desirable to use, together with them, a vulcanization
accelerator, an accelerator activator or an activating agent to accelerate
the crosslinking reaction of sulfur. Appropriate combination, amounts
used, etc. can be determined by referring to, for example, the above
literature.
When an organic peroxide is used as a crosslinking agent, it is preferable
to use therewith a crosslinking aid such as functional monomer or the
like.
The selection of the crosslinking agent to be used is desirably made in
thorough consideration of the properties of the rubbery polymer in
Component (ii). The selection must be made by paying attention to the
followings.
When the rubbery polymer in Component (ii) is highly unsaturated, there is
selected a crosslinking agent effective to highly unsaturated rubbers, for
example, a sulfur type, a resin crosslinking agent or the like, whereby
the rubbery polymer can be predominantly crosslinked.
When the rubbery polymer in Component (ii) is an essentially saturated
polymer, particularly an .alpha.-monoolefin copolymer rubber or a rubber
of low unsaturation, thorough investigation is made on the amount of
crosslinking agent used to enable crosslinking; in this case, however,
there is a restriction that the crosslinking degree of the rubbery polymer
cannot be made sufficiently high. As the method for basic solution
thereto, there can be mentioned a method in which there is used, as the
rubbery polymer, a rubbery polymer containing a functional group such as
carboxyl group, acid anhydride group, hydroxyl group, epoxy group, halogen
group, amino group, isocyanate group, sulfonyl group, sulfonate group or
the like and further there is used, as the crosslinking agent, a compound
reactive with the functional group. The functional group-containing
rubbery polymer can be obtained, for example, by subjecting a functional
group-containing monomer to copolymerization or by introducing a
functional group into a rubbery polymer by a known graft reaction. The
compound used as a crosslinking agent is a polyfunctional compound capable
of effecting a substitution reaction with the functional group in the
rubbery polymer and can be a low-molecular weight compound or a
high-molecular, weight compound.
Specifically, a carboxyl group-containing rubbery polymer can be easily
crosslinked by a diamino compound, bisoxazoline, a diepoxy compound, a
diol compound or the like.
A diamino compound is an effective crosslinking agent for a maleic
anhydride group-containing rubbery polymer.
A dithio compound or bismaleimide can be used as a crosslinking agent for a
rubbery polymer having unsaturated portions.
A diamino compound is effective when the rubbery polymer is an acrylic
rubber or a polymer composed mainly of an acrylic acid ester.
A dithiol compound is an effective crosslinking agent when the rubbery
polymer is a chlorinated polymer (e.g. chlorinated polyethylene).
In Elastomer Composition (II) using Component (i'), the functional group
added to the rubbery polymer may be the same as introduced into Component
(i'). In this case, there may also occur crosslinking of Component (i')
with the polyfunctional compound used as a crosslinking agent.
This, however, can be solved, for example, by reducing the amount of
functional group in Component (i') or by adding an appropriate amount of
the hydrogenated diene polymerized as a starting material for Component
(i') (modified hydrogenated diene polymer).
The thus obtained Elastomer Composition (II) has a structure in which an
appropriate amount of Component (i') has been grafted on a crosslinked
rubbery polymer. Such a structure often shows highest dynamic properties
and provides a preferable composition of this invention.
The amount of crosslinking agent used can be determined appropriately
depending upon the properties required for desired final composition. The
selection of appropriate crosslinking system and the determination of the
amount are desirably made by referring to, for example, the above
literature. Usually, there can be appropriately used a crosslinking agent
in a range of 0.1-8 parts by weight per 100 parts by weight of the rubbery
polymer, a vulcanization accelerator in a range of 0.1-10 parts by weight,
an accelerator activator in a range of 0.5-10 parts by weight, an
activating agent in a range of 0.5-10 parts by weight and a crosslinking
aid in a range of 0.1-10 parts by weight. It is necessary that at least
10% by weight, preferably at least 30% by weight, more preferably at least
40% by weight, of the rubbery polymer used as Component (ii) has been
allowed to gel. When the gelation degree of the rubbery polymer is less
than 10% by weight, the improvement in dynamic properties due to
crosslinking is insufficient.
The gel content of the rubbery polymer is taken as a gel content of a
crosslinked rubbery polymer obtained by subjecting the rubbery polymer
alone to the same crosslinking as applied in the preparation of Elastomer
Composition (II). The gel content is determined usually by subjecting the
above crosslinked rubbery polymer to extraction with cyclohexane at
70.degree. C. for 4 hours, followed by calculation. When the rubbery
polymer is insoluble in cyclohexane, a good solvent for the rubbery
polymer is used.
In the thermoplastic elastomer composition of this invention comprising
Component (i) or (i') and Component (ii), when Component (ii) comprises at
least 10% by weight of a thermoplastic resin, there can be obtained an
elastomer composition [Elastomer Composition (III)] having excellent
dynamic properties, by subjecting Component (i) or (i') and Component (ii)
to reaction in the presence of a crosslinking agent capable of
crosslinking even Component (i) or (i'), while applying shear deformation,
to allow at least 10% by weight of the total of the rubbery polymer and
Component (i) or (i') to gel.
Elastomer Composition (III) can be obtained by subjecting Elastomer
Composition (I) wherein Component (ii) comprises a thermoplastic resin in
an amount of at least 10% by weight, to shear deformation (melt-mixing) in
the presence of a compound capable of crosslinking Component (i) or (i')
and a rubbery polymer as another component of Component (ii), to allow at
least 10% by weight of the total of Component (i) or (i') and the rubbery
polymer.
Thus, Elastomer Composition (III) is characterized by using Component (i)
or (i') as a rubber component.
In Elastomer Composition (III), it is essential that a thermoplastic resin
be used as Component (ii) in an amount of at least 10% by weight,
preferably 10-80% by weight, more preferably 15-70% by weight. When the
amount is less than 10% by weight, the resulting composition has no
thermoplasticity and poor processability.
Preferable as the thermopalstic resin used in Elastomer Composition (III)
are olefin-based crystalline thermoplastic polymers such as polyethylene,
polypropylene, polybutene-1 and the like, and crystalline thermoplastic
polymers such as polyamide, polyester, polyamide elastomer, polyester
elastomer and the like.
Since in Elastomer Composition (III), Component (i) or (i') which is an
essentially saturated olefin block copolymer, is used as a rubber
component, the crosslinking agent is preferably a system consisting of an
organic peroxide and a crosslinking aid.
The organic peroxide preferably has a one-minute half-life temperature of
150.degree. C. or more. Such an organic peroxide includes, for example,
2,5-dimethyl-2,5-dibenzoylperoxyhexane, n-butyl
4,4-di-tert-butylperoxyvalerate, dicumyl peroxide, tert-butyl
peroxybenzoate, di-tert-butylperoxy-di-isopropylbenzene, tert-butylcumyl
peroxide, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, di-tert-butyl
peroxide, and 2,5-dimethyl-2,5-di-tert-butylperoxyhexyne-3.
The crosslinking aid used is preferably a radical-polymerizable monomer or
a radical-crosslinkable polymer. Such a crosslinking aid includes
divinylbenzene, bismaleimide, trimethylolpropane triacrylate,
trimethylolpropane methacrylate, pentaerythritol triacrylate, aluminum
acrylate, aluminum methacrylate, zinc methacrylate, zinc acrylate,
magnesium acrylate, magnesium methacrylate, triallyl isocyanurate,
triallyl cyanurate, triallyl trimellitate, diallyl phthalate, diallyl
chlorendate, liquid polybutadiene, liquid poly(1,2-butadiene), etc. These
crosslinking aids can be used alone or in admixture of two or more.
Besides the crosslinking aid, there can be used a radical-accepting
compound in combination. In this case, a composition of better properties
can be obtained.
The radical-accepting compound is a compound which is rich in reactivity
with free radical and accepts the free radical to act itself as a radical
source or a compound which decomposes to generate a free radical. It
includes sulfur, sulfur compounds, p-quinone derivatives, p-quinonedioxime
derivatives, thiol group-containing compounds and the like which are
preferably used. Specifically, preferred are sulfur, p-quinonedioxime,
p,p'-dibenzoylquinonedioxime, hexafluoroisopropylidenebisphenol,
dihydroxybenzophenone, hydroquinone, 2,4,6-trimercapto-S-triazine,
dibenzothiazyl disulfide, tetramethylthiuram disulfide,
dipentamethylenethiuram tetrasulfide and the like. These may be used alone
or in admixture of two or more.
The amount of organic peroxide used is preferably 0.001-0.1 mole in terms
of active oxygen amount, per 100 parts by weight of Component (i) or (i')
or the total of Component (i) or (i') and other rubbery polymer. When the
amount is less than 0.001 mole, there takes place no sufficient
crosslinking. The use of organic peroxide in an amount of more than 0.1
mole gives no further crosslinking, is not economical, and tends to invite
side reactions such as polymer decomposition and the like.
The crosslinking aid is used preferably in such an amount that the amount
of unsaturated double bonds in crosslinking aid becomes 1/4 to 40
equivalents per equivalent of the active oxygen in the organic peroxide
used in combination. When the amount is less than 1/4 equivalent, the
improvement in crosslinking efficiency due to the addition of crosslinking
aid is negligibly small and no sufficient crosslinking takes place. When
the amount is more than 40 equivalents, no further crosslinking is
obtained and such an amount is uneconomical.
In using the radical-accepting compound, the amount (mole) used is usually
1/20 to 2 equivalents per equivalent of the active oxygen in the organic
peroxide used in combination. The use of the radical-accepting compound in
an amount less than 1/20 equivalent shows no addition effect. The use in
an amount of more than 2 equivalents gives no further effect, is
uneconomical and, in some cases, invites significant reduction in
crosslinking efficiency and produces local gelation.
The gel content in Component (i) or (i') or in Component (i) or (i') and
rubbery polymer in Component (ii) is calculated using the method described
with respect to Elastomer Composition (II).
Elastomer Composition (IV) of this invention is such a composition that in
Elastomer Composition (I), Component (ii) is a polyolefin resin and that a
nonaromatic process oil is contained as Component (iii).
Component (ii) in the Elastomer Composition (IV) is at least one resinous
polymer selected from polyolefin resins. Preferable examples of Component
(ii) are polypropylene, polyethylene, polymethylpentene and polybutene-1.
The proportions of Component (i) or (i') and Component (ii) in Elastomer
Composition (IV) are usually 10-90 parts by weight, preferably 20-80 parts
by weight, more preferably 25-75 parts by weight of Component (i) or (i'),
and usually 90-10 parts by weight, preferably 80-20 parts by weight, more
preferably 75-25 parts by weight of Component (ii) [Component (i) or
(i')+Component (ii)=100 parts by weight].
When the proportion of Component (i) or (i') is less than 10 parts by
weight, the resulting composition has poor elasticity. When the proportion
is more than 90 parts by weight, the resulting composition has low heat
resistance.
Component (i) or (i') used in Elastomer Composition (IV) is particularly
preferably a block copolymer consisting of 10-70% by weight of Block C and
90-30% by weight of Block D, the 1,2-vinyl content in Block C being 15% or
less and the 1,2-vinyl content in Block D being 22-55%, or a modified
hydrogenated diene polymer obtained by adding a functional group to the
above block copolymer.
Component (iii) used in Elastomer Composition (IV) is a non-aromatic
process oil. Preferable examples of the oil is a paraffinic process oil or
a naphthenic process oil.
The amount of Component (iii) used is usually 1-300 parts by weight,
preferably 5-200 parts by weight, more preferably 10-150 parts by weight
per 100 parts by weight of the total of Component (i) or (i') and
Component (ii).
When the amount is less than 1 part by weight, no softening effect is
obtained. When the amount is more than 300 parts by weight, there occurs
oil bleeding and significant reduction in strength.
Elastomer Composition (V) of this invention is obtained by subjecting
Elastomer Composition (IV) to reaction in the presence of a component for
crosslinking Component (i) or (i') contained in Elastomer Composition
(IV), while applying shear deformation, to allow at least 10% by weight of
Component (i) or (i') to gel. Elastomer Composition (V), as compared with
Elastomer Composition (IV), is characterized by being superior to the
latter in compression set, in particular.
As to the individual components constituting Elastomer Composition (V) and
their appropriate amounts used, the same description as in Elastomer
Composition (IV) applies. The component for crosslinking Component (i) or
(i') used in Elastomer Composition (V) is preferably a system consisting
of an organic peroxide, a crosslinking aid and a radical-accepting
compound. Typical examples of such a system and the amount used are the
same as described as to Elastomer Composition (III).
In Elastomer Composition (V), it is necessary that at least 10% by weight
of Component (i) or (i') has been allowed to gel, and it is desirable that
preferably at least 15% by weight, more preferably at least 20% by weight
of Component (i) or (i') has been allowed to gel. When the gel content in
Component (i) or (i') is less than 10% by weight, there is obtained no
sufficient improvement in elasticity by crosslinking. The gel content is
calculated by the method described as to Elastomer Composition (II).
Elastomer Composition (VI) comprises Component (i) or (i'), a polyolefin
resin and an olefin copolymer rubber both as Component (ii), and a
non-aromatic process oil as Component (iii).
Preferable examples of Component (i) or (i'), the polyolefin resin in
Component (ii), and Component (iii) are the same as those described in
Elastomer Composition (IV). Elastomer Composition (VI) is a combination of
Elastomer Composition (IV) and an olefin copolymer rubber and is an
elastomer composition of low hardness. The olefin copolymer rubber used in
Component (ii) of Elastomer Composition (VI) is a rubbery polymer composed
mainly of an olefin compound, and preferable examples of the olefin
copolymer rubber are ethylene-propylene rubber, ethylene-propylene-diene
rubber, ethylene-butene rubber, ethylene-butene-diene rubber,
ethylene-acrylate rubber, chlorinated polyethylene, chlorosulfonated
polyethylene, hydrogenation product of styrene-butadiene rubber, and
hydrogenation product of nitrile rubber.
These olefin copolymer rubbers can be used alone or in admixture.
The amounts of the individual components used in Elastomer Composition (VI)
are as follows. Component (i) or (i') are used in an amount of 5-95 parts
by weight, preferably 15-85 parts preferably 20-80 parts by weight. When
the amount is less than 5 parts by weight, the resulting composition has
poor dynamic properties and insufficient strengths. When the amount is
more than 95 parts by weight, the composition has reduced heat resistance
in some cases.
The ratio of the polyolefin resin and the olefin copolymer rubber in
Component (ii) is usually polyolefin resin/olefin copolymer rubber=10-90%
by weight/90-10% by weight, preferably 15-85% by weight/85-15% by weight,
more preferably 20-80% by weight/80-20% by weight.
When the polyolefin resin is less than 10% by weight and the olefin
copolymer rubber is more than 90% by weight, the resulting composition has
poor dynamic properties. When the polyolefin resin is more than 90% by
weight and the olefin copolymer rubber is less than 10% by weight, the
composition is insufficient in hardness (low hardness) because the content
of the olefin copolymer rubber in the composition is too low.
The amount of Component (ii) used in Elastomer Composition (VI) is usually
95-5 parts by weight, preferably 85-15 parts by weight, more preferably
80-20 parts by weight [Component (i) or (i')+Component (ii) =100 parts by
weight]. When the amount is more than 95 parts by weight, the resulting
composition tends to have poor dynamic properties. When the amount is less
than 5 parts by weight, the composition is insufficient in hardness (low
hardness) and has reduced heat resistance.
The amount of Component (iii) used in Elastomer Composition (VI) is 1-400
parts by weight, preferably 5-300 parts by weight, more preferably 10-250
parts by weight per 100 parts by weight of the total of Component (i) or
(i') and Component (ii). When the amount is less than 1 part by weight, no
softening effect can be expected. When the amount is more than 400 parts
by weight, oil bleeding and reduction in strength are striking.
Elastomer Composition (VII) is obtained by subjecting Elastomer Composition
(VI) to reaction in the presence of a crosslinking agent for crosslinking
the olefin copolymer rubber contained in Elastomer Composition (VI), while
applying shear deformation, to allow at least 10% by weight of the olefin
copolymer rubber to gel. Elastomer Composition (VII), as compared with
Elastomer Composition (VI), is characterized by being superior to the
latter, in dynamic strengths and compression set, in particular.
As to the individual components constituting Elastomer Composition (VII)
and their appropriate amounts used, the same description as to Elastomer
Composition (VI) applies. Preferable examples of the olefin copolymer
rubber as part of Component (ii) are ethylene-propylene-diene rubber,
ethylene-butene-diene rubber and partial hydrogenation products of these
rubbers, all containing appropriate amounts of unsaturations in the
molecule. As the crosslinking agent for crosslinking the olefin copolymer
rubber as part of Component (ii), there are used those ordinarily used in
crosslinking rubbers [they are described in detail as to Elastomer
Composition (II)].
In Elastomer Composition (VII), there are preferably used sulfur type
crosslinking agents, resin crosslinking agents (e.g.
alkylphenol-formaldehyde resin), combinations of an organic peroxide and a
crosslinking aid, described in detail as to Elastomer Composition (III),
etc.
The amount of crosslinking agent used can be appropriately determined
depending upon the properties required for the desired final composition.
Specific examples are described in Elastomer Composition (II).
Preferable examples of the organic peroxide, crosslinking aid and
radical-accepting compound and their amounts are the same as described as
to Elastomer Composition (III).
In Elastomer Composition (VII), it is necessary that at least 10% by weight
of the olefin copolymer rubber as part of Component (ii) has been allowed
to gel, and it is desirable that preferably at least 40% by weight, more
preferably at least 80% by weight of the olefin copolymer rubber has been
allowed to gel. When the gel content in olefin copolymer rubber is less
than 10% by weight, the resulting composition has low elasticity.
The gel content is calculated by the method described as to Elastomer
Composition (II).
Elastomer Composition (VIII) is an elastomer composition which comprises,
as essential components, Component (i) or (i') used in Elastomer
Composition (I) and (ii) a component consisting of (A) an olefin polymer
in or to which a carboxylic acid derivative and/or an epoxy derivative has
been copolymerized or grafted, or a polymer obtained by bonding, to the
olefin polymer, other polymer in a graft or block form, and (B) at least
one polymer selected from the group consisting of polyamide polymers and
polyester polymers, and which further comprises, as an optional component,
0-400 parts by weight, per 100 parts by weight of the total of Component
(i) or (i') and the (ii) component, of (iii) a softening agent.
In Elastomer Composition (VIII), the (A) component of the (ii) component is
used in order to improve the compatibility between the (B) component of
the (ii) component and Component (i) or (i'), and is an olefin polymer
having grafted thereon or copolymerized therewith a functional
group-containing compound (e.g. carboxylic acid derivative and/or epoxy
derivative) the olefin polymer having other polymer bonded thereto in a
graft or block form.
Preferable examples of the carboxylic acid derivative in the (A) component
are acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic
anhydride and itaconic anhydride.
Preferable examples of the epoxy derivative are glycidyl acrylate, glycidyl
methacrylate and allyl glydicyl ether.
The olefin polymer with or on which a carboxylic acid derivative and/or an
epoxy derivative is to be copolymerized or grafted, includes a polymer
composed mainly of an .alpha.-monoolefin of 2-4 carbon atoms, and a
polymer obtained by hydrogenating a polymer composed mainly of a
conjugated diene. Specific examples of the olefin polymer are
polyethylene, polypropylene, propylene-ethylene copolymer,
propylene-butene copolymer, hydrogenated polybutadiene and hydrogenated
butadiene-styrene copolymer.
The said other polymer to be bonded in a graft or block form to the olefin
polymer having copolymerized therewith or grafted thereon a carboxylic
acid derivative and/or an epoxy derivative is used in order to control the
reactivity of the functional group-containing compound or to control the
miscibility. The type of the said other polymer is not critical, and there
is appropriately used an acrylic polymer, a styrene polymer or the like.
Preferable examples of the (A) component are maleic anhydride-modified
polyethylene, maleic anhydride-modified polypropylene, maleic
anhydride-modified ethylene-propylene copolymer, ethylene-glycidyl
methacrylate copolymer, allyl glycidyl ether-modified polyethylene, allyl
glycidyl ether-modified polypropylene, allyl glycidyl ether-modified
ethylene-propylene copolymer, ethylene-glycidyl methacrylate copolymer
having grafted thereon poly(methyl methacrylate), ethylene-glycidyl
methacrylate copolymer having grafted thereon polystyrene, and
ethylene-glycidyl methacrylate copolymer having grafted thereon
styrene-acrylonitrile copolymer.
The (B) component in the (ii) component is at least one polymer selected
from the group consisting of polyamide polymers and polyester polymers.
Preferable examples of the (B) component are polyamides such as nylon 6,
nylon 6,6, nylon 4,6, nylon 11, nylon 12 and the like; thermoplastic
polyamide elastomers; polyesters such as poly(ethylene terephthalate),
poly(butylene terephthalate) and the like; and thermoplastic polyester
elastomers.
The proportions of the (A) component and the (B) component in the (ii)
component are such that the (A) component is usually 0.5-50% by weight,
preferably 0.5-40% by weight, more preferably 0.5-30% by weight. When the
proportion of the (A) component in the (ii) component is less than 0.5% by
weight, the improvement in miscibility is insufficient. When the
proportion is more than 50% by weight, no further effect is obtained and
such a proportion is uneconomical.
Elastomer Composition (VIII) essentially comprising the (A) component and
the (B) component as to (ii) component, may further contain other compound
(e.g. rubbery compound) as the (ii) component. The use of rubbery compound
is effective to reduce composition hardness, and accordingly is convenient
for providing a soft composition.
In using the rubbery compound as the (ii) component, the properties of the
rubbery compound are not critical, but it is advantageous that the (ii)
component comprises at least 10% by weight, preferably 15% by weight, more
preferably 20% by weight of the (B) component.
When the proportion of the (B) component is less than 10% by weight, the
addition of rubbery compound reduces the heat reduction of composition in
some cases. The rubbery compound can be crosslinked as necessary.
Crosslinking of rubbery compound can be effected by, after the addition of
the rubbery compound, adding a crosslinking agent during kneading and then
carrying out crosslinking dynamically. Alternatively, there can be used a
rubbery compound appropriately crosslinked beforehand. Crosslinking of
rubbery compound is preferable because it tends to improve the compression
set of the composition.
The proportions of Component (i) or (i') and the (ii) component in
Elastomer Composition (VIII) are usually 5-95 parts by weight [Component
(i) or (i')]/95-5 parts by weight [the (ii) component], preferably 10-90
parts by weight/90-10 parts by weight, more preferably 15-85 parts by
weight/85-15 parts by weight [Component (i) or (i')+the (ii) component=100
parts by weight]. When Component (i) or (i') is less than 5 parts by
weight and the (ii) component is more than 95 parts by weight, the
resulting composition is hard and poor in flexibility. When Component (i)
or (i') is more than 95% by weight and the (ii) component is less than 5
parts by weight, the composition has insufficient heat resistance.
As the softening agent (iii) used in Elastomer Composition (VIII), there is
used a plasticizer for polyamide or polyester, or a non-aromatic process
oil.
As the plasticizer, there are preferably used a phthalic acid ester, a
trimellitic acid ester, a phosphoric acid ester, etc. As the non-aromatic
process oil, there are preferably used a paraffinic oil and a naphthenic
oil. The softening agent (iii) is optionally used when it is necessary to
allow Elastomer Composition (VIII) to have a low hardness. It is used in
an amount of usually 0-400 parts by weight, preferably 5-300 parts by
weight, more preferably 10-250 parts by weight per 100 parts by weight of
the total of Component (i) or (i') and the (ii) component. When it is used
in an amount of more than 400 parts by weight, bleeding of softening agent
and reduction in composition strength are striking.
Thermoplastic Elastomer Composition (I) to (VIII) of this invention can
comprise, as necessary, various additives, for example, stabilizers such
as antioxidant, heat stabilizer, ultraviolet absorber, copper harm
preventing agent and the like, inorganic fillers such as silica, talc,
carbon, calcium carbonate, magnesium carbonate, glass fiber and the like,
and organic fillers such as wood flour, cork powder, cellulose powder,
rubber powder and the like.
Thermoplastic Elastomer Compositions (I) to (III) can further comprise a
softening agent such as plasticizer, oil or the like.
In producing the thermoplastic elastomer composition of this invention,
there can be used a conventional kneading apparatus, for example, a
batchwise kneading apparatus (e.g. rubber mill, Bradender mixer, Banbury
mixer, pressure kneader), or a continuous kneading apparatus (e.g. single
screw extruder, twin screw extruder). From the standpoint of productivity,
there is most preferred a system enabling continuous production, i.e. a
twin screw extruder or a combination of a batchwise kneading apparatus and
a twin screw extruder.
In the actual kneading by twin screw extruder, all components are kneaded
at one time, or some components are kneaded and the remaining components
are added in the middle. When a liquid softening agent is used in a large
amount, it is desirable to add the softening agent under pressure in the
middle of extruder after the solid components have been melted. When it is
necessary to add a softening agent and a crosslinking agent in the middle
of the extruder, their addition order is not critical but, to reduce the
increase in load caused by crosslinking, it is desirable to add the
crosslinking agent after addition of the softening agent under pressure.
The thermoplastic elastomer composition of this invention is a novel
composition using E-EB type TPE which is intrisically an excellent
thermoplastic elastomer and yet which has not been put into practical
application, and can satisfy various industrial requirements.
The modified hydrogenated diene polymer of this invention has an olefin
structure but has excellent compatibility with polyamides, polyesters,
etc. Accordingly, compositions having excellent properties can be obtained
by blending the above polymer with various other polymers.
Specific examples of the application of the thermoplastic elastomer
composition of this invention include parts for automobiles and vehicles,
such as skin material for interior parts, rack-and-pinion boot, bellows,
vacuum connector, tube, side body molding, head rest, regulator, arm rest,
shift lever boot, weather strip, air spoiler, suspension boot, belt cover,
wheel cover, nob, bumper, site shield, bumper molding and the like;
industrial parts such as hydraulic hose, air tube, rubber hose, out-cover,
various gaskets, container, 0-ring, packing material, key board material
and the like; color tiles; floor material; furnitures; skin material for
household electric appliances; vibration insulators; and sporting goods
such as skin material for grip and the like.
Also, the thermoplastic elastomer composition of this invention is an
excellent shape memory resin and can be used as mechanical parts, joint
material, etc.
This invention is described in more detail below referring to Examples.
However, this invention is not restricted to these Examples.
In the Examples, parts and % are by weight unless otherwise specified.
In the Examples, tensile strength, elongation at break, elongation set at
100% extension, compression set and hardness were measured in accordance
with JIS K 6301. Gel content of rubber was measured by the above-mentioned
method.
EXAMPLES 1-10 AND COMPARATIVE EXAMPLES 1-4 [EXAMPLES ON ELASTOMER
COMPOSITIONS (I) TO (III)]
(i) A hydrogenated diene polymer and (ii) a thermoplastic polymer and/or a
rubbery polymer were fed into a laboratory plastomill controlled at
190.degree. C., in accordance with the compounding recipe shown in Table
1, and were mixed at 80 rpm for 10 minutes. The mixture was taken out and
made into a sheet on a heated roll. The sheet was press-molded to prepare
a square sheet of 10 cm.times.10 cm. The sheet was cut by a dumbbell
cutter to prepare test pieces for measurement.
When a crosslinking agent was used, it was added after confirming the
complete melting of the (i) component and the (ii) component. After the
addition of the crosslinking agent, mixing at 80 rpm was continued up to 3
minutes after the torque meter fit to the laboratory plastomill had showed
a maximum shaft torque; then, the mixture was taken out. In most cases,
the time from addition of crosslinking agent to taking-out of mixture was
20 minutes or less.
The results are shown in Table 1.
In Table 1, Examples 1-5 are on Elastomer Compositions (I) of this
invention; Examples 7-8 are on Elastomer Compositions (II) of this
invention; and Examples 9-10 are on Elastomer Compositions (III) of this
invention. It is appreciated that each of these Elastomer Compositions was
a composition showing the excellent properties of the hydrogenated diene
polymer (i).
In contrast, Comparative Examples 1-2 are on compositions using no
hydrogenated diene polymer; and these compositions had a low elongation at
break, a high hardness and a low elongation set.
Comparative Example 3 is on the (i) component alone; and it had a low
strength at break and was not practical.
Comparative Example 3 is on a composition using, as the (i) component, a
hydrogenated styrene/butadiene/styrene block copolymer (SEBS, Kraton
G1650); and the composition was inferior in elongation, compression set,
etc.
EXAMPLES 11-14 AND COMPARATIVE EXAMPLES 5-7 [EXAMPLES ON ELASTOMER
COMPOSITIONS (IV)]
A composition of pellet form was prepared in accordance with the
compounding recipe shown in Table 2, using a twin screw extruder of
L/D=32.5 (PCM-45 manufactured by Ikegai Seisakusho K.K.). The pellets
were injection-molded to prepare a square sheet of 10 cm.times.10 cm. The
sheet was cut by a dumbbell cutter to prepare test pieces for measurement.
In the preparation of the composition in the twin screw extruder,
Component (i) and Component (ii) were dry-blended; the blend was passed
through the extruder; and Component (iii) was pressure-fed into the middle
of the extruder in a state that said blend was a uniform melt. The results
are shown in Table 2.
As is clear from Table 2, the Elastomer Compositions (IV) of this invention
are elastomers having a low hardness, excellent elasticity and excellent
dynamic properties.
In contrast, Comparative Example 5 is on a composition containing a
softening agent in an amount larger than specified; and the composition
showed severe oil bleeding and was unable to mold. Comparative Examples
6-7 are on compositions using Kraton G1650 in place of the Component (i)
of this invention; and these compositions had a hardness and dynamic
properties about equal to those of the Elastomer Compositions of this
invention, but had a low compression set and accordingly were unsuited for
use as an elastomer.
EXAMPLES 15-18 AND COMPARATIVE EXAMPLES 8-10 [EXAMPLES ON ELASTOMER
COMPOSITIONS (V)]
A composition of pellet form was prepared in accordance with the
compounding recipe shown in Table 3, using a twin screw extruder (TEX-44
manufactured by Nippon Seiko K.K.). The pellets were injection-molded to
prepare a square sheet of 10 cm.times.10 cm. The sheet was cut by a
dumbbell cutter to prepare test pieces for measurement. In the preparation
of the composition in the twin screw extruder, Component (i), Component
(ii) and a crosslinking aid were dry-blended; the blend was passed through
the extruder; and pressure feeding of Component (iii) and addition of a
crosslinking agent (an organic peroxide) were effected at the middle of
the extruder in a state that said blend was a uniform melt. Incidentally,
the order of the pressure feeding of Component (iii) and the addition of
the crosslinking agent is not critical. The results are shown in Table 3.
As is clear from Table 3, the Elastomer Compositions (V) of this invention
were improved in compression set, in particular and accordingly were
improved in elastomer properties. In contrast, Comparative Example 8 is on
a composition containing a crosslinking agent in an amount larger than
specified; and the composition showed severe gelation of Component (i) and
was unable to injection-mold. Comparative Examples 9-10 are on
compositions using Kraton G1650 in place of the Component (i) of this
invention; and the compositions had a hardness and dynamic properties
about equal to those of the Elastomer Compositions of this invention, but
were insufficient in improvement of compression set.
EXAMPLES 19-22 AND COMPARATIVE EXAMPLES 11-13 [EXAMPLES ON ELASTOMER
COMPOSITIONS (VI)]
A composition of pellet form was prepared in accordance with the
compounding recipe shown in Table 4, using a twin screw extruder (PCM-45
manufactured by Ikegai Seisakusho K.K.). The pellets were injection-molded
to prepare a square sheet of 10 cm.times.10 cm. The sheet was cut by a
dumbbell cutter to prepare test pieces for measurement. In the preparation
of the composition in the twin screw extruder, Component (i) and Component
(ii) were dry-blended; the blend was passed through the twin screw
extruder; and Component (iii) was pressure-fed into the middle of the
extruder in a state that said blend was a uniform melt. The results are
shown in Table 4.
As is clear from Table 4, the Elastomer Compositions (VI) of this invention
had a very low hardness and a sufficient compression set, and accordingly
were suited for use as an elastomer.
In contrast, Comparative Example 11 is on a composition containing an oil
in an amount larger than specified; and the composition gave severe oil
bleeding and was unable to mold. Comparative Examples 12-13 are on
compositions using Kraton G1650 in place of the Component (i) of this
invention; and the compositions had a hardness and dynamic properties
about equal to those of the Elastomer Compositions of this invention, but
had a low compression set and accordingly were unsuited for use as an
elastomer.
EXAMPLES 23-26 AND COMPARATIVE EXAMPLES 14-16 [EXAMPLES ON ELASTOMER
COMPOSITIONS (VI)]
A composition of pellet form was prepared in accordance with the
compounding recipe shown in Table 5, using a twin screw extruder (TEX-44
manufactured by Nippon Seiko K.K.). The pellets were injection-molded to
prepare a square sheet of 10 cm.times.10 cm. The sheet was cut by a
dumbbell cutter to prepare test pieces for measurement.
The results are shown in Table 5. As is clear from Table 5, the Elastomer
Compositions (VII) of this invention were elastomer compositions of
extremely low hardness as not seen in conventional thermoplastic
elastomers and were excellent in dynamic properties and compression set,
in particular.
In contrast, Comparative Example 14 is on a composition containing a
softening agent in an amount larger than specified; and the composition
caused severe oil bleeding. Comparative Example 15 is on a composition
containing no Component (i); and the composition had poor dynamic
properties and was unsuited for practical use. Comparative Example 16 is
on a composition using Kraton G1650 in place of the Component (i) of this
invention; and the composition had dynamic properties and a hardness about
equal to those of the Elastomer Compositions of this invention, but had a
low compression set.
EXAMPLES 27-30 AND COMPARATIVE EXAMPLES 17-19 [EXAMPLES ON ELASTOMER
COMPOSITIONS (VI)]
A composition of pellet form was prepared in accordance with the
compounding recipe shown in Table 6, using a twin screw extruder (PCM-45
manufactured by Ikegai Seisakusho K.K.). The pellets were injection-molded
to prepare a square sheet of 10 cm.times.10 cm. The sheet was cut by a
dumbbell cutter to prepare test pieces for measurement.
The results are shown in Table 6. As is clear from Table 6, the Elastomer
Compositions (VIII) of this invention had excellent dynamic properties and
an excellent compression set.
In contrast, Comparative Example 17 is on a composition containing no
Component (A) and had poor dynamic properties.
Comparative Examples 18-19 are on compositions using Kraton G1650 in place
of Component (i); and the compositions had dynamic properties about equal
to those of the Elastomer Compositions of this invention, but had a low
compression set and were unsuited as an elastomer.
TABLE 1
Example Comparative Example 1 2 3 4 5 6 7 8 9 10 1 2 3 4
Compounding recipe Component (i) Type BL-1*.sup.5
BL-1*.sup.5 BL-1*.sup.5 BL-2*.sup.9 BL-1*.sup.5 BL-2*.sup.9 BL-2*.sup.9
BL-2*.sup.9 BL-3*.sup.14 BL-3*.sup.14 -- -- BL-2*.sup.9 SEBS*.sup.15
parts 60 60 40 90 5 80 70 60 70 40 -- -- 100 60 Component (ii)
Thermoplastic resin Type PE*.sup.6 PP*.sup.7 PP*.sup.7 EA*.sup.10
PP*.sup.7 -- -- PE*.sup.6 PP*.sup.7 PP*.sup.7 PE*.sup.6 PP*.sup.7 --
PP*.sup.7 Parts 40 40 30 10 40 -- -- 10 30 30 40 40 -- 40 Rubbery
polymer Type -- -- EBM*.sup.8 -- EPR*.sup.11 EPDM*.sup.12 MAH-EP*.sup.13
EPDM*.sup.12 -- EPR*.sup.11 EMB*.sup.8 EPR*.sup.11 -- -- Parts -- -- 30
-- 55 20 30 30 -- 30 60 60 -- -- Crosslinking Agent Sulfur -- -- -- --
-- 0.4 -- 0.5 -- -- -- -- -- -- BBS*.sup.1 -- -- -- -- -- 0.2 --
0.25 -- -- -- -- -- -- MBTS*.sup.2 -- -- -- -- -- 0.2 -- 0.25 --
-- -- -- -- -- Triethyltetramine -- -- -- -- -- -- 1.0 -- -- -- -- --
-- -- t-BPO*.sup.3 -- -- -- -- -- -- -- -- 1.0 1.0 -- -- -- --
TAC*.sup.4 -- -- -- -- -- -- -- -- 1.2 1.2 -- -- -- -- Physical
properties Tensile strength (Kg/cm.sup.2) 110 150 100 250 140 240
200 200 190 140 100 110 50 232 Elongation at break (%) 800 910
750 800 820 880 860 860 700 750 340 140 1,000 210
Elongation set at 100% 33 36 37 13 34 14 12 11 13 16 45 56 10 45
extension (%) Hardness (JIS A) 85 88 75 75 86 72 69 72 68 65 95 96 66 98
Gel content of rubber (%) -- -- -- -- -- 90 90 92 90 93 -- -- --
--
TABLE 1'
______________________________________
1,2-Vinyl 1,2-Vinyl Number-average
Hydro-
content in
content in
molecular weight
genation
Block C Block D C/D/C degree
(%) (%) (.times. 10.sup.3)
(%)
______________________________________
*5 12 45 30/140/30 98
*9 13 80 60/120/60 97
*14 10 56 25/200/25 98
______________________________________
Note:-
*.sup.1 Ntert-butyl-2-benzothiazolesulfenamide
*.sup.2 2Bis-benzothiazyl disulfide
*.sup.3 Ditert-butyl peroxide
*.sup.4 Triallyl cyanurate
*.sup.5 A hydrogenated diene polymer shown in Table
*.sup.6 ZF51, a polyethylene manufactured by Mitsubishi Petrochemical Co.
Ltd.
*.sup.7 MA7, a polypropylene manufactured by Mitsubishi Petrochemical Co.
Ltd.
*.sup.8 2041P, an ethylenebutene rubber manufactured by Japan Synthetic
Rubber Co., Ltd.
*.sup.9 A hydrogenated diene polymer shown in Table
*.sup.10 A graft polymer obtained by grafting an acrylonitrilestyrene
random copolymer onto an ethylenebutene copolymer
*.sup.11 EP02P manufactured by Japan Synthetic Rubber Co., Ltd.
*.sup.12 EP57P manufactured by Japan Synthetic Rubber Co., Ltd.
*.sup.13 An ethylenepropylene copolymer rubber grafted with 2% of maleic
anhydride
*.sup.14 A hydrogenated diene polymer shown in Table
*.sup. 15 Kraton G1650 manufactured by Shell.
TABLE 2
__________________________________________________________________________
Comparative
Comparative
Comparative
Example 11
Example 12
Example 13
Example 14
Example 5
Example 6
Example
__________________________________________________________________________
7
Compounding recipe
Component (i)
Type BL-4*.sup.16
BL-5*.sup.17
BL-6*.sup.18
BL-6*.sup.18
BL-4*.sup.16
SEBS*.sup.15
SEBS*.sup.15
Parts 60 60 70 80 60 60 70
Component (ii)
Thermoplastic resin
Type PP*.sup.7
TPX*.sup.19
PP*.sup.7
PP*.sup.7
PP*.sup.7
PP*.sup.7
PP*.sup.7
Parts 40 40 30 20 40 40 30
Rubbery polymer
Type -- -- -- -- -- -- --
Parts -- -- -- -- -- -- --
Component (iii)
Softening agent
Type PW-90*.sup.20
PW-90*.sup.20
PW-90*.sup.20
PW-90*.sup.20
PW-90*.sup.20
PW-90*.sup.20
PW-90*.sup.20
Parts 70 70 50 100 350 70 50
Physical properties
Tensile strength (Kg/cm.sup.2)
240 230 260 180 Molding
210 190
Elongation at break (%)
750 680 800 950 was 640 750
Compression set (%)*.sup.21
45 42 45 40 impossible
75 80
Hardness (JIS A)
80 83 78 60 due to oil
80 77
bleading.
__________________________________________________________________________
TABLE 2'
______________________________________
1,2-Vinyl 1,2-Vinyl Number-average
Hydro-
content in content in
molecular weight
genation
Block C Block D C/D/C degree
(%) (%) (.times. 10.sup.3)
(%)
______________________________________
*16 12 35 45/210/45 98
*17 12 33 75/350/75 98
*18 13 40 60/180/60 98
______________________________________
Note:-
*16, *17 and *18: Hydrogenated diene polymers shown in Table
*.sup.19 A polymethylpentene manufactured by Mitsui Petrochemical
Industries, Ltd.
*.sup.20 A paraffinic oil manufactured by Idemitsu Petrochemical
*.sup.21 Measured under conditions of 70.degree. C. .times. 22 hours
TABLE 3
__________________________________________________________________________
Comparative
Comparative
Comparative
Example 15
Example 16
Example 17
Example 18
Example 8
Example
Example
__________________________________________________________________________
10
Compounding recipe
Component (i)
Type BL-4*.sup.16
BL-5*.sup.17
BL-6*.sup.18
BL-6*.sup.18
BL-4*.sup.16
SEBS*.sup.15
SEBS*.sup.15
Parts 60 60 70 70 60 60 70
Component (ii)
Thermoplastic resin
Type PP*.sup.7
PP*.sup.7
PP*.sup.7
PP*.sup.7
PP*.sup.7
PP*.sup.7
PP*.sup.7
Parts 40 40 30 30 40 40 30
Rubbery polymer
Type -- -- -- -- -- -- --
Parts -- -- -- -- -- -- --
Component (iii)
Type PW-90*.sup. 20
PW-90*.sup.20
PW-90*.sup.20
PW-90*.sup.20
PW-90*.sup.20
PW-90*.sup.20
PW-90*.sup.20
Parts 70 70 30 100 70 70 100
Crosslinking agent
Kayahexa AD*.sup.22
0.4 0.4 0.5 0.5 5 0.4 0.5
BMI*.sup.23 0.7 0.7 0.8
0.8 10 0.7 0.8
HQ*.sup.24 0.05
0.05
0.06
0.06
1 -- --
Physical properties
Tensile strength (Kg/cm.sup.2)
270 290 280 200 Moldability
230 200
Elongation at break (%)
640 600 650 700 was poor.
560 550
Compression set (%)*.sup.21
32 31 30 30 53 50
Hardness (JIS A)
82 83 79 62 84 79
Gel content of rubber (%)*.sup.25
35 40 35 38 40 38
__________________________________________________________________________
Note:
*.sup.7 Same as in Note of Table 1
*.sup.8 Same as in Note of Table 1
*.sup.16- *.sup.21 as in Note of Table 2
*.sup.22 2,5Dimethyl-2,5-di(tert-butylperoxy)hexane manufactured by Kayak
Noury Co., Ltd.
*.sup.23 Bismaleimide
*.sup.24 Hydroquinone
*.sup.25 Cyclohexane gel content
TABLE 4
__________________________________________________________________________
Comparative
Comparative
Comparative
Example 19
Example 20
Example 21
Example 22
Example 11
Example 12
Example
__________________________________________________________________________
13
Compounding recipe
Component (i)
Type BL-4*.sup.16
BL-5*.sup.17
BL-6*.sup.18
BL-6*.sup.18
BL-4*.sup.16
SEBS*.sup.15
SEBS*.sup.15
Parts 40 40 40 40 40 40 40
Component (ii)
Thermoplastic resin
Type PP*.sup.7
PP*.sup.7
PP*.sup.7
PP*.sup.7
PP*.sup.7
PP*.sup.7
PP*.sup.7
Parts 20 20 20 20 20 20 20
Rubbery polymer
Type EPDM*.sup.26
EPDM*.sup.26
EPDM*.sup.26
EPDM*.sup.26
EPDM*.sup.26
EPDM*.sup.26
EPDM*.sup.26
Parts 40 40 40 40 40 40 40
Component (iii)
Type PW-90*.sup.20
PW-90*.sup.20
PW-90*.sup.20
PW-90*.sup.20
PW-90*.sup.20
PW-90*.sup.20
PW-90*.sup.20
Parts 100 150 200 250 500 100 200
Physical properties
Tensile strength (Kg/cm.sup.2)
100 80 60 40 Molding
85 40
Elongation at break (%)
800 850 900 1,000 was 700 900
Compression set (%)*.sup.21
50 48 43 41 impossible
80 85
Hardness *JIS A)
50 40 30 20 due to oil
50 30
bleeding.
__________________________________________________________________________
Note:
*.sup.7 Same as in Note of Table 1
*.sup.15 Same as in Note of Table 1
*.sup.16- *.sup.18 & *.sup.20- *.sup.21 Same as in Note of Table 2
*.sup.26 EP98A manufactured by Japan Synthetic Rubber Co., Ltd.
TABLE 5
__________________________________________________________________________
Comparative
Comparative
Comparative
Example 23
Example 24
Example 25
Example 26
Example 14
Example
Example
__________________________________________________________________________
16
Compounding recipe
Component (i)
Type BL-4*.sup.16
BL-5*.sup.17
BL-6*.sup.18
BL-6*.sup.18
BL-4*.sup.16
-- SEBS*.sup.15
Parts 40 40 40 40 40 -- 40
Component (ii)
Thermoplastic resin
Type PP*.sup.7
PP*.sup.7
PP*.sup.7
PP*.sup.7
PP*.sup.7
PP*.sup.7
PP*.sup.7
Parts 20 20 20 20 20 40 20
Rubbery polymer
Type EPDM*.sup.26
EPDM*.sup.26
EPDM*.sup.26
EPDM*.sup.26
EPDM*.sup.26
EPDM*.sup.26
EPDM*.sup.26
Parts 40 40 40 40 40 60 40
Component (iii)
Type PW-90*.sup.20
PW-90*.sup.20
PW-90*.sup.20
PW-90*.sup.20
PW-90*.sup.20
PW-90*.sup.20
PW-90*.sup.20
Parts 100 150 200 250 500 150 200
Crosslinking agent
Kayahexa AD*.sup.22
2.0 2.0 -- 2.5 2.0 2.5 2.0
BMI*.sup.23 3.0 3.0 -- 4.0 3.0 4.0 3.0
HQ*.sup.24 0.4 0.4 -- 0.5 0.4 0.6 0.4
SP1045*.sup.27 -- -- 6.0 -- -- -- --
SnCl.sub.2 2H.sub.2 O
-- -- 0.5 -- -- -- --
Physical properties
Tensile strength (Kg/cm.sup.2)
140 110 85 65 Molding
15 65
Elongation at break (%)
650 680 700 750 was 500 600
Compression set (%)*.sup.21
28 27 26 26 impossible
35 45
Hardness (JIS A)
53 42 30 21 due to oil
45 28
Gel content of rubber (%)*.sup.25
90 90 95 98 bleeding.
98 90
__________________________________________________________________________
Note:
*.sup.7 Same as in Note of Table 1
*.sup.15 Same as in Note of Table 1
*.sup.16- *.sup.18 & *.sup.20- *.sup.21 Same as in Note of Table 2
*.sup.22- *.sup.25 Same as in Note of Table 3
*.sup.26 Same as in Note of Table 4
*.sup.27 A vulcanizing agent of resin, manufactured by Nihon Shokubai
Kagaku Kogyo Co., Ltd.
TABLE 6
__________________________________________________________________________
Comparative
Comparative
Comparative
Example 27
Example 28
Example 29
Example 30
Example 17
Example
Example
__________________________________________________________________________
19
Compounding recipe
Component (i)
Type BL-4*.sup.16
BL-5*.sup.17
BL-6*.sup.18
BL-6*.sup.18
BL-4*.sup.16
SEBS*.sup.15
SEBS*.sup.15
Parts 60 70 50 40 60 50 40
Component (ii)
Component (A)
Type PE-MAH*.sup.28
A4200*.sup.29
PP-MAH*.sup.30
A4200*.sup.29
-- PP-MAH*.sup.30
A4200*.sup.29
Parts 10 10 5 5 -- 5 5
Component (B)
Type PA6*.sup.31
PBT*.sup.32
TAPE*.sup.33
TPEE*.sup.34
PA6*.sup.31
TAPE*.sup.33
TAPE*.sup.33
Parts 30 20 45 45 40 45 45
Rubbery polymer
Type -- -- -- EPDM*.sup.26
-- -- EPDM*.sup.26
Parts -- -- -- 10 -- -- 10
Physical properties
Tensile strength (Kg/cm.sup.2)
350 360 300 260 120 280 240
Elongation at break (%)
650 530 600 650 100 560 600
Compression set (%)*.sup.21
55 50 45 45 55 75 78
Hardness (JIS A)
98 95 93 90 98 93 90
__________________________________________________________________________
Note:
*.sup.15-18 & .sup.21 Same as in Note of Table 1
*.sup.26 Same as in Note of Table 4
*.sup.28 Maleic anhydridemodified polyethylene
*.sup.29 Modiper A4200 manufactured by Nippon Oils and Fats Co., Ltd.
*.sup.30 Maleic anhydridemodified polypropylene
*.sup.31 Nylon 6
*.sup.32 Poly(butylene terephthalate)
*.sup.33 Polyamide elastomer
*.sup.34 Polyester elastomer
EXAMPLES 31-33 (PREPARATION OF MODIFIED HYDROGENATED DIENE POLYMERS)
A modified hydrogenated diene polymer was prepared in accordance with the
compounding recipe shown in Table 7, and made into test pieces in the same
manner as in Example 1.
The test pieces were used for measurement of physical properties in
accordance with JIS K 6301. The results are shown in Table 7.
EXAMPLES 34-48 AND COMPARATIVE EXAMPLES 10-11 (PREPARATION OF MODIFIED
HYDROGENATED DIENE POLYMERS OR THERMOPLASTIC POLYMER COMPOSITIONS)
Test pieces were prepared in the same manner as in Example 1, using the
compounding recipe shown in Table 7.
The test pieces were used for measurement of physical properties in
accordance with JIS K 6301. The results are shown in Table 7.
In Table 7, Examples 31-33 and 41-44 are Examples for preparing the
modified hydrogenated diene polymers of this invention, and Examples 34-40
and 45-48 are Examples for preparing the thermoplastic polymer
compositions of this invention. Each of these polymers and compositions
had excellent physical properties.
Comparative Example 10 is on a composition using a hydrogenated
styrene/butadiene/styrene block polymer to which 3% of maleic anhdyride
has been added; and the composition had dynamic properties about equal to
those of the compositions of this invention, but had a high melt viscosity
and accordingly poor processability.
Comparative Example 11 is on the maleic anhydride-modified SEBS itself,
used in Comparative Example 10; and the modified SEBS had physical
properties about equal to those of the modified hydrogenated diene
polymers of this invention, but had drawbacks of SEBS as mentioned in
Comparative Example 10, i.e. high melt viscosity and poor processability.
The hydrogenated block polymers BL-1, BL-2 and BL-3 used in some of the
Examples were prepared as follows.
BL-1 was prepared according to the following procedure. Into a 10-liter
autoclave were fed 4,800 g of dry cyclohexane and 180 g of purified
butadiene. Thereinto was injected, as a polymerization catalyst, about 4.5
cm.sup.3 of a hexane solution containing 14% of n-butyllithium, in a high
purity nitrogen current. The mixture was subjected to polymerization at
70.degree. C. for 1 hour. The reaction mixture was cooled to 50.degree.
C., and 1,700 ppm of THF and 420 g of purified butadiene were added. The
mixture was subjected to polymerization at 70.degree.-80.degree. C. for 1
hour. Then, 4.9 cm.sup.3 of a 11% methyldichlorosilane solution was added
to subject the polymer to coupling. 30 cm.sup.3 of a 10%
di-tert-butyl-p-cresol solution, 10 ml of a 14% n-butyllithium solution,
0.3 g of diethyldichlorotitanium and 8 cm.sup.3 of a 15%
diethylchloroaluminum chloroaluminum solution were added at 70.degree. C.,
and hydrogen gas of 10 kg/cm.sup.2 was passed therethrough with sufficient
stirring. After about 2 hours of hydrogenation reaction, the contents in
the autoclave were taken out, subjected to steam stripping, and roll-dried
to obtain BL-1.
BL-2 and BL-3 were prepared in accordance with the above procedure.
The properties of BL-1, BL-2 and BL-3 are shown in Table 8.
TABLE 7
__________________________________________________________________________
Example 31
Example 32
Example 33
Example 34
Example 35
Example
Example
__________________________________________________________________________
37
Materials used for preparation of
Component (i) (parts)
Hydrogenated block polymer
Type BL-1*.sup.5
BL-2*.sup.9
BL-3*.sup.14
-- -- -- --
Amount
100 100 100 -- -- -- --
Functional group-containing
Type GAE*.sup.35
PAB*.sup.36
MA*.sup.37
-- -- -- --
monomer Amount
3 3 3 -- -- -- --
Organic peroxide
Type t-BPO*.sup.38
t-BPO*.sup.38
t-BPO*.sup.38
-- -- -- --
Amount
0.2 0.2 0.2 -- -- -- --
Compounding recipe of composition (parts)
Component (i) Type -- -- -- 1 1 2 3
Amount
-- -- -- 60 70 30 5
Component (ii)
Thermoplastic resin
Type -- -- -- PA12*.sup.43
PBT*.sup.44
PA12*.sup.43
PA12*.sup.43
Amount
-- -- -- 40 30 30 50
Rubbery polymer
Type -- -- -- -- -- EPDM*.sup.45
EPDM*.sup.45
Amount
-- -- -- -- -- 40 45
Compound recipe of crosslinking
agent (parts)
Vulcanizing agent for resin*.sup.39
-- -- -- -- -- 1.0 1.0
SnCl.sub.2 dihydrate -- -- -- -- -- 0.2 0.2
PBO*.sup.40 -- -- -- -- -- -- 0.5
tert-PBO*.sup.38 -- -- -- -- 0.8 -- --
TAC*.sup.41 -- -- -- -- 1.0 -- --
BMI*.sup.42 -- -- -- -- -- -- --
Physical properties
Tensile strength (Kg/cm.sup.2)
230 160 70 300 310 240 200
Elongation at break (%)
1,000 1,000 1,000 450 440 480 400
Elongation set at 100% extension (%)
11 8 5 20 33 25 30
Hardness (JIS A) 88 75 66 94 100 88 92
Retention of tensile strength at 80.degree. C. (%)
40 35 25 70 70 65 75
__________________________________________________________________________
Compar-
ative Ex-
Example 38
Example 39
Example 40
ample 10
Example 41
Example
Example
__________________________________________________________________________
43
Materials used for preparation of
Component (i) (parts)
Hydrogenated block polymer
Type -- -- -- -- BL-2*.sup.9
BL-2*.sup.9
BL-2*.sup.9
Amount
-- -- -- -- 100 100 100
Functional group-containing
Type -- -- -- -- MDMAE*.sup.49
MAH*.sup.50
HEMA*.sup.51
monomer Amount
-- -- -- -- 4 3 4
Organic peroxide
Type -- -- -- -- t-BPO*.sup.38
t-BPO*.sup.38
t-BPO*.sup.38
Amount
-- -- -- -- 0.3 0.2 0.2
Compounding recipe of composition (parts)
Component (i) Type 1 1 3 SEBS*.sup.48
-- -- --
Amount
40 40 80 60 -- -- --
Component (ii)
Thermoplastic resin
Type TPEE*.sup.46
TPAE*.sup.47
TPEE*.sup.46
PA12*.sup.13
-- -- --
Amount
60 60 20 40 -- -- --
Rubbery polymer
Type -- -- -- -- -- -- --
Amount
-- -- -- -- -- -- --
Compound recipe of crosslinking
agent (parts)
Vulcanizing agent for resin*.sup.39
-- -- -- -- -- -- --
SnCl.sub.2 dihydrate -- -- -- -- -- -- --
PBO*.sup.40 -- -- -- -- -- -- --
tert-PBO*.sup.38 -- 0.8 -- -- -- -- --
TAC*.sup.41 -- -- -- -- -- -- --
BMI*.sup.42 -- 1.0 -- -- -- -- --
Physical properties
Tensile strength (Kg/cm.sup. 2)
160 240 140 320 165 155 163
Elongation at break (%)
780 530 1,000 420 850 900 950
Elongation set at 100% extension (%)
18 23 19 21 8 8 8
Hardness (JIS A) 90 95 84 100 75 76 75
Retention of tensile strength at 80.degree. C. (%)
75 75 55 65 36 34 35
__________________________________________________________________________
Compar-
ative
Example 44
Example 45
Example 46
Example 47
Example
Example
__________________________________________________________________________
11
Materials used for preparation of
Component (i) (parts)
Hydrogenated block polymer
Type BL-2*.sup.9
-- -- -- -- SEBS*.sup.48
Amount
100 -- -- -- -- 100
Functional group-containing
Type Cl-ST*.sup.52
-- -- -- -- --
monomer Amount
4 -- -- -- -- --
Organic peroxide Type t-BPO*.sup.38
-- -- -- -- --
Amount
0.3 -- -- -- -- --
Compounding recipe of composition (parts)
Component (i) Type -- 1 2 13 14 --
Amount
-- 60 60 60 40 --
Component (ii)
Thermoplastic resin Type -- PA12*.sup.43
PA12*.sup.43
TPAE*.sup.47
PP*.sup.53
--
Amount
-- 40 40 40 20
Rubbery polymer Type -- -- -- -- Cl-PE*.sup.54
--
Amount
-- -- -- -- 40 --
Compound recipe of crosslinking
agent (parts)
Vulcanizing agent for resin*.sup.39
-- -- -- -- -- --
SnCl.sub.2 dihydrate -- -- -- -- -- --
PBO*.sup.40 -- -- -- -- -- --
tert-PBO*.sup.38 -- -- -- -- -- --
TAC*.sup.41 -- -- -- -- -- --
BMI*.sup.42 -- -- -- -- -- --
Physical properties
Tensile strength (Kg/cm.sup. 2)
163 250 270 185 180 300
Elongation at break (%) 880 460 490 780 600 450
Elongation set at 100% extension (%)
8 22 21 18 16 6
Hardness (JIS A) 76 95 95 92 86 85
Retention of tensile strength at 80.degree. C. (%)
35 72 75 70 55 35
__________________________________________________________________________
Note:
*.sup.5, *.sup.9 and *.sup.14 Same as in Note of Table 1
*.sup.35 Allyl glycidyl ether
*.sup.36 N(p-carboxyphenylmaleimide)
*.sup.37 Maleic acid
*.sup.38 Ditert-butyl peroxide
*.sup.39 An alkylphenolformaldehyde resin
*.sup.40 Bisoxazoline
*.sup.41 Triallyl isocyanurate
*.sup.42 Bismaleimide
*.sup.43 Rilsan AMNO, a nylon 12 manufactured by Toray Industries
Incorporated
*.sup.44 Toray PBT 1401X06, a poly(butylene terephthalate) manufactured b
Toray Industries Incorporated
*.sup.45 JSR EP57P, an ethylenepropylene rubber manufactured by Japan
Synthetic Rubber Co., Ltd.
*.sup.46 PIBIFLEX 46 CM, a polyester elastomer manufactured by Dutral
*.sup.47 Grilux A250, a polyamide elastomer manufactured by DAINIPPON INK
& CHEMICALS, INC.
*.sup.48 A modified SEBS obtained by grafting Kraton G1650 manufactured b
Shell K. K. with 3% of maleic anhydride
*.sup.49 Dimethylaminoethyl methacrylate
*.sup.50 Maleic anhydride
*.sup.51 Hydroxyethyl methacrylate
*.sup.52 pChlorostyrene
*.sup.53 Polypropylene (MA7)
*.sup.54 Chlorinated polyethylene rubber
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